Unit 1 Mod 2 Rates of Reaction

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RATES OF REACTION
Collision theory
1. For a reaction to occur, particles MUST collide
2. Particles must collide with at least a certain minimum amount of
energy (activation energy)
3. Particles must collide with the correct orientation
All three conditions can be collectively called EFFECTIVE
COLLISIONS
Rate of reactions are generally measured in mol dm-3 s-1
Rate equation
A rate equation shows the effect of concentration of the reactants to the
initial rate of reaction.
For a general reaction A + B product
general rate equation initial rate =k[A]m[B]n
initial rate = rate of reaction at the beginning of the reaction
k = rate constant
m = order of reaction with respect to reactant A
n = order of reaction with respect to reactant B
total order of reaction = m + n
Orders of reaction (shows how the initial rate is affected by any one
particular reactant)
Zero order implies that the rate of reaction is not affected by concentration. i.e.
the rate does NOT change even if the concentration increases or decreases.
First order implies that the rate of reaction increases proportionally with the
change in concentration. e.g. if concentration of a reactant doubles, the rate
ALSO DOUBLES, if the concentration triples, the rate ALSO TRIPLES etc
Second order implies that the rate of reaction increases with the SQUARE of
the change in concentration i.e. if the concentration doubles, the rate
QUADRUPLES, if the concentration triples, the rate increase NINE FOLD .

Unit 1 Mod 2 Rates of Reaction

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You also need to know both zero AND first order reactions using
concentration vs time graphs.

Sample calculation on determining orders of reaction, the value and units

of the rate constant and the initial rate of a reaction
The following results were obtained for a reaction between A and B
Expt #
Concentration /mol dm-3
Initial rate /
mol dm-3 s-1
[A]
[B]
1
0.5
1
2
2
0.5
2
8
3
0.5
3
18
4
1
3
36
5
2
3
72
6
2
4
?

Unit 1 Mod 2 Rates of Reaction

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a) to find the order of reaction with respect to B, you would

compare expt # 1 and 2 as [A] is constant and [B] varies
As [B] doubles, the initial rate increases 4 fold, therefore rate increase
with the SQUARE of the change in concentration i.e. 2nd order therefore
n=2
b) to find the order of reaction with respect to A, you would
compare expt # 4 and 5, [B] is constant and [A] varies
As [A] doubles, initial rate doubles, therefore it is a proportional change,
which means 1st order i.e. m = 1
Total order of reaction = 2 + 1 = 3
c) To determine the rate of reaction for expt #6
You can use ANY expt # from 1 to 5 e.g. expt #3
Specific rate equation Initial rate = k[A] 1[B]2
For expt #3 18 = k[0.5]1[2]2
18
0.5 x 4

= k =4

To determine the units of k mol dm-3 s-1 = k x mol dm-3 x (mol dm-3)2
mol dm-3 s-1 = k x mol3 dm-9
mol dm-3 s-1 = k
mol3 dm-9
therefore units of k = mol -2 dm6 s-1

Unit 1 Mod 2 Rates of Reaction

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Checkpoint A

a) What is the order of reaction with respect to:i) A2

[1]

ii) B2 [1]

iii) The overall order of the reaction [1]

.
b) Write the rate equation for the reaction [1]
.
c) Calculate the value of the rate constant and its units [2]

d) If an experiment was conducted with the [A] as 0.4 and the [B] as 0.3,
calculate the initial rate of the reaction. [1]

Unit 1 Mod 2 Rates of Reaction

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Rate determining step and reaction mechanism

All chemical reactions occur as a series of small steps from beginning to
end. Reaction mechanisms can only be determined experimentally.
All mechanisms have a rate determining step which is the slowest step
in the reaction. Rate determining steps (RDS) would have an order of
either 1 or 2. The FAST step in any reaction mechanism would have an
order of zero.

Example Calculate the orders of reaction with respect to A and B,

determine the rate equation and propose a mechanism consistent with
the kinetics.
order wrt A = 1 order wrt B = 0
rate equation initial rate = k[A][B]0 initial rate = k[A]
proposed mechanism
A2 2A (slow) 2A + B2 2AB (fast)

CHECKPOINT B

a) Use the data on the left to determine the order of reaction with respect
to i) S2O82- and ii ) Ib) The total order of reaction

Unit 1 Mod 2 Rates of Reaction

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c) the rate equation for the reaction

Half-life
The time taken for a reaction to go to half completion, it is called the
half-life. First order reactions have CONSTANT half lives.
equation (1) kt = ln (A0 / A)
equation (2) kt1/2 = 0.693

The decay of radioactive

isotopes is a first order
reaction

k = rate constant
t = time
A0 = initial concentration or original percentage (usually 100%)
A = current concentration or current percentage
t1/2 = time of half life
Sample calculation of half life

The half life of radium is 1590 years. How long will it take for a sample
of radium to decay to 10% of its original radioactivity?
This means t1/2 = 1590
First using equation (2)
kt1/2 = 0.693 k x 1590 = 0.693 k = 4.36 x 10-4 year-1
Then using equation (1)
4.36 x 10-4 x t = ln (100/10) t = 5280 years
Checkpoint C
1. Calculate the percentage of radioactivity remaining after 280 years if
its half-life is 28 years (will show this one in class)
2. A sample decays by 50% in 45 minutes. What is the half life of the
sample?
3. An isotope of caesium has a half -life of 30 years). If 4.2 mg of
cesium-137 disintegrates over a period of 90 years, how many mg of
cesium-137 would remain?

Unit 1 Mod 2 Rates of Reaction

Effect of temperature and catalysts on rate of reaction

Maxwell-Boltzman distribution curve

The effect on temperature

The effect of a catalyst

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Unit 1 Mod 2 Rates of Reaction

Very few molecules have a very low

energy level, most molecules have
an average energy level and again
very few molecules have a very high
energy level

At a higher temperature, more

molecules (it doubles for every 10 C)
have the activation energy for the
reaction. Therefore a faster rate of
reaction. Note the area under the curve
remains the SAME!!

A catalyst LOWERS the activation

energy needed so more molecules
would now have the required amount of
energy for the reaction and thus a faster
rate of reaction.

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